Production of alkyl phenols from petroleum hydrocarbons



tertiary alkyl phenols and other valuable com- PETBOLEUM HYDBOCABBONSHyyrn E. Bnc, Roselle, and Reuben Schuler, Elizabeth, N. 1., asaig'norato Standard Oil Development Company, a corporation of Delaware NoDrawing. Application June SerialNo. 617,604

20 Claims. (01. 200-154) This invention relates to the production ofalbl phenols from petroleum hydrocarbons and more 1 especially, to themanufacture of secondary and 5 pounds from unsaturated hydrocarbonsformed in cracking petrole um oils.

I Bylthe methods herein described, compositions highly suitable for useas fungicides, disinfect- I ants, germicides and for therapeuticpurposes generally may be prepared by treating crackedpetroleumfractions with phenols under suitable reaction conditions. a Thisinvention will be fully understood from th 1200 can followingillustrative example:

Example-'1 distillate boiling between 60 and 72- C. obtained. irom. thenaphtha produced in cracking a gas oil at 150 poundsper square inch 1pressure are mixed with 370 grams of phenol (CoI-IsOH). To this mixture216 cc. of 95% sulfuric-acid are added slowly with stirring and coolm o.a t below about 60? the temperature of the mixture 0. When the additionof acid is completed the mixture is stirred at room temperature (withoutheating'or cooling) for about 2 hours. It is then heated on a water bathto about 100 C. to remove theunreacted petroleum fraction.

v 900 cc. of. a residue consisting largely of g sulfonated alkylphenolic compounds are thus obtained. This residue is diluted .withwater to obtainl800 cc. of diluted mixture which contains about 38 gramsof water.

of total sulfuric acid per 100 cc.

This mixture is then heated in a sealed autoclave at 180 C. for 2 hoursto hydrolyae the sulfonated compounds. On cooling a top oily layer'and.a bottom acidlayer separate. The oil i consists mainly of a mixture'of secondary and '45 tertiary hexyl phenols. The remaining 5% of alkaliinsoluble product is a mixture of corresponding hexyl phenyl ethers andpossibly high boiling polymers of the original oleilnes. The alkyl phe-"I nols may be purified by distillation with steam or under vacuum, orbyother suitable methods. The I washed oily product may be distilled invacuo. The fraction distilling below 150 C. at 1 mm. pressure-consistsalmost completely of alkyl pheflnols. The resid 55.,ble in alkali.

ue isa viscous tarry mass, insolu- Other hydroxy aromatic compounds suchas cresol, resorcinol, hydroquinone,- pyrogallol and the like may beused instead of the phenol in the 1 above example to producecorresponding alkylated phenolic derivatives.

This process may be used for the production of secondary and tertiaryalkyl phenols from petroleum fractions containing oleflnes of more than2 carbonatoms. The petroleum fractions containing oleflnes frompropylene to oetylene, inclusive, represent the preferred range for thisprocess.

Products especially suitable.for use as fungicides and containingisopropyl phenols and secondaryjand tertiary butyl and amyl phenols maybe obtained from light cracked petroleum fractions having the boilingrange of the correspond- 8 hydrocarbons. For example, cracked petroleumfractions boiling between about -20 and Y +20 0., corresponding to thebutane series of hydrocarbons, may be used to prepare a mixture ofsecondary and tertiarybutyl phenols. This prodnot is an exceptionallypowerful fungicide. Products suitable for fungicidal use may generallybe obtained with cracked petroleum fractions boiling within the range ofabout and +50 C. Other fractions boiling within a narrower range such as+10 to +50 0., corresponding to the pentane series, may be used ifdesired. It is preferred. in order to obtain satisfactory reaction ratesto conduct the reaction of phenol and cracked petroleum fractions atsufficiently elevated pressure to maintain the petroleum fraction inliquid phase during the reaction. A temperature of about 50 to C. ispreferred for this reaction, although higher or lower to peratures maybe used.

Products containing alkyl phenols preferred for therapeutic andgermicidal uses are obtained from the higher boiling fractions. Thefractions boiling between 60. and 72 C., and more broadly between about40-and- 0., are especially suitable for the preparation of powerfulgermicides. However, this invention is not to be limited to anyparticular boiling range of the petroleum fractions used, as those ofstill higher and lower boiling ranges may be used in the hereindescribed processes for the production of valuable products.

The sulfonated alkyl phenolic derivatives prepared as described in thefirst reaction of the above example also represent a new and valuableproduct. These sulfonated reaction products are substantially completelywater soluble and are valuable for use as water soluble germicides,

wetting agents, emulsifiers, fungicides and oxidation inhibitors. Thesesulfonated reaction products may also be neutralized with an alkali toproduce water soluble salts of similar charac- I teristics.

maximumv germicidal activity for B. tuphosus,v

while heptyl and octyl phenols, of less germicidal value than hexylphenol for this bacterium, are much more effective than hexyl phenol inkilling Staphylococcus aureus. The mixed alkyl phenols prepared frompetroleum'are therefore suitable as a general germicide for a variety ofbacteria.

Similarly the crude butyl phenols prepared from cracked petroleumfractions contain both secondary and tertiary butyl phenols togetherwith oily polymers and ethers, which also possess certain advantageswhen this product is used in horticultural sprays or wood impregnants.

The production of alkylated phenolic products directly from crackedpetroleum fractions also permits marked savings inthe cost and ease ofpreparation. Alkylated products are obtained in' substantiallytheoretical yields based on both the oleflnes and phenols used. Productscontaining '90 to 95% of alkyl phenols are obtained with correspondinglydecreased formation of alkyl aryl ethers which are less eifective asfungicides and germicides and usually represent asubstan-' tial loss ofthe reagents used. The best yields obtainable by reaction of phenolswith pure oleflnes are usuall not reater than 50 or 60 and y g fectivegermicidal concentration a mixture of the products obtained contain notless than 40 to of alkyl aryl ethers. In addition, such pure oleflnesare normally obtained by dehydration of alcohols which in turn areproduced by the absorption of oleflnes from cracked gases with sulfuricacid. A loss of about 50% of the This invention is not to be limitedhowever to this particular method of operation. The reaction may also beconducted according to the method described in United States applicationSer. No. 522.177 filed March 12, 1931, by I-lfyym E.- Buc, in whichalkyl phenols are produced with- 0:: substantial sulfonation of reagentsor produ s.

Mixed phenols corresponding to the oleflnes present in light crackedpetroleum fractions may also be prepared by reaction of a phenol withsuitable sulfuric acid extracts of cracked petroleum gases and lightdistillates. Such extracts, known as reactive acid liquors, may containsub- I stantlally only propylenes; or butylenes and higher oleflnes; orpropylenes and higher oleilnes, according to the concentration ofsulfuric acid and. the procedure used in extracting the oleflnes fromthe petroleum fractions according to the known art. For example, thephenol and acid liquor may be'mixed and additional strong or acidmaybeadded witheoolalkyl group prepared by reactionoi' a phenol with ing tobring the ratio of total sulfuric acid to water in the mixture within asuitable range for' the formation of alkyl phenols, say above about 93%vof sulfuric acid, based on acid and water present, and the processcontinued as described a in the above examples. The acid liquors mayalso be hydrolyzed to yield secondary and tertiary alcoholscorresponding to the olefines present. These alcohols may then becondensed with phenols to form the corresponding l to .phenols byreaction in the presence of sulfuric acid or other suitable condensationagent according to the process described in tic-pending applicationSerial Number 593,414, filed February 10, 1932 by Beamer. is

The term "alkyl phenol" isv used to designate a hydroxy aromatic such asphenol, cl, resorcinol, hydroquinone, pyrogallol. naphthol and the likecontaining one or more alkyl groups attached to the aromatic ring. Theproduct may contain 20 alkyl phenols, alkylaryl ethers, and mixedcompounds having the characteristic radicals of both phenol and ether.The products are character-- ized by branched alkyl groups; that is,alkyl radicalscontaining a carbon. atom attached to 25 the aromaticradical,.or to a connecting element such as oxygen, and to two or threecarbon atoms in thealkyl group. Such compounds are classifled assecondary or tertiary alkyl phenolic derivatives, respectively. I

' This invention is not to be limited to anyexamples or theories or theoperation of our procsee, which have been presented solely for purpose V'of illustration, but only by the following claims in which we wish toclaim all novelty.

We claim: 1. Germlcidal composition containing in an efalkyl phenolscontaining alkyl groups of more than 4 carbon atoms corresponding to theolefines' 40 of a petroleum fraction. i

2. Germicidal composition containing in an effective germicidalconcentration .a mixture of alkyl phenols of more than 4 carbon atoms inthe 5 cracked petroleum oleflnes.

3. Germicidal and fungicidal composition containing in eflectiveconcentration a reaction prodnot of a phenol with the olefines of acracked petroleum fraction boiling within theme of --60 and +60 C., saidproduct including i mixture of alkyl phenols of more than 4 carbon atomsin the alkyl group of pronounced fungicidal activity.

4. Germicidal composition containing in an effective germicidalconcentration a mixture of alkyl phenols produced by reaction of aphenol with the oleiines of a cracked troleum fraction boiling betweenabout 60 and $2 0.

6.. Germicidal composition containing in an to eifective germicidalconcentration a mixture of alkyl phenols ofpronounced germicidalactivity comprising a reaction product of a phenol with the oleflnes ofa cracked petroleum fraction boiling within the range of 40 to C.

6. Germicidal composition containing in an effective germicidalconcentration a product consisting of a mixture of alkyl phenols derivedfromcracked petroleum oleflnes and a phenol. said oleflnes comprisingthose of the amylene to 00- 70 vtylene series, said product comprisingsecondary tilting 01' a mixture of alkyl phenols derived from 76 crackedpetroleum oleflnes and a phenol. said oleflnes comprising those, of'the'amylene to ctylene series, said product comprising secondary andtertiary alkyl phenols and a minor proportion of alkyl aryl ethers.

8. Composition of matter consisting of a water soluble mixture ofsulfonated alkyl phenols obtained by reaction of the oleflnes of morethan 4 carbon atoms in a cracked petroleum fraction with a phenol andsulfuric acid.

9. Composition of matter consisting of a water soluble mixture of saltsof sulfonated alkyl phenolsrobtained by reaction of the oleflnes in acracked petroleum fraction with a phenol, and sulfuric acid.

10. Process for preparing alkyl phenols comprising reacting a phenolwith a petroleum fraction containing unsaturated hydrocarbons.

11. Process for preparing alkyl phenols comprising reacting a phenolwith a cracked petroleum fraction in the presence of strong sulfuricacid.

12. Process for obtaining valuable derivatives from phenols comprisingbringing a mixture of a phenol and a liquid cracked petroleum fractioncontaining unsaturated hydrocarbons of more than 2 carbon atoms intoreaction in the presence of strong sulfuric acid and forming a reactionproduct comprising suli'onated alkyl phenolic derivatives.

13. Process for obtaining valuable derivatives from phenols comprisingbringing a mixture of a phenol and a cracked petroleum fractioncontaining unsaturated hydrocarbons of more than 2 carbon atoms intoreaction in the presence of strong sulfuric acid and forming areaction'product comprising sulfonsted alkyl phenolic derivatives, andsubsequently converting said sulfonated phenolic derivatives into thecorrespondingsalts by neutralization with an alkali.

14.- Process for obtaining valuable derivatives .-sulfonated alkylphenolic derivatives are converted into the corresponding alkyl phenolicderivatives by hydrolysis.

17. Composition of matter consisting largely of a mixture of alkylphenols derived from cracked petroleum olefines and a phenol, saidoleilnes corresponding to those of a cracked petroleum fraction boilingover a rangeof at least 12 on the centigrade scale and being within theamylene to octylene series.

18. Germicidal composition containing in an eifective germicidalconcentration a mixture of alkyl phenols having an alkyl phenol withfive to eight carbon atoms in said alkyl group.

19. Process for preparing alkylated phenolic bodies which comprisesreacting a phenol with a cracked petroleum fraction which predominatelycontains hydrocarbons of four carbon atoms to the molecule.

20. Process for preparing alkyl phenols which comprises reacting aphenol with a cracked petroleum fraction which contains'predominatelyhydrocarbons oi four carbon atoms to the molecule and which alsocontains tertiary butylene in the presence of a mineral acid condensingagent.

HY'YM E. BUC. 40 REUBEN SCHULER.

,DISCLAIMER 2,045,749.Hyym E. Buc, Roselle, N. J., and Reuben Sclwlar,Elizabeth, N. J.

Pnonuc'non or Amr'rn Pnmnons mou-Pn'rnonmnu Hnmocannone. Patent datedJune 30, 1936. D' aimer. filed April. 3, 1940, by the assignee,

Standard Oil Development Company.

Hereby disclaims from the scoge of claim 18 of said Letters Patent anymixture of alkyl phenols except mixtures w 'ch contain two difierentalklyl phenol molecules m which an alkgl group of one of the said alkylphenol molecu es difiers from any alkgl group in t e other of said alkylphenol molecules either in the total number'of car on atoms in each ofthe alkyl groups or in the number of carbon atoms connected to thecarbon atom in each alkyl group 'oining it to the phenolic group.

- [017M411 Gazette April 23, 1940.} p

